CN101503212A - Method for preparing mesoporous titanium dioxide - Google Patents
Method for preparing mesoporous titanium dioxide Download PDFInfo
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- CN101503212A CN101503212A CNA200910047155XA CN200910047155A CN101503212A CN 101503212 A CN101503212 A CN 101503212A CN A200910047155X A CNA200910047155X A CN A200910047155XA CN 200910047155 A CN200910047155 A CN 200910047155A CN 101503212 A CN101503212 A CN 101503212A
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Abstract
The invention relates to a method for preparing mesoporous titanium dioxide, which comprises the following steps: adopting a silanes compound as a template agent; enabling the silanes compound to form silicon oxide during the calcining process; and attaching the silicon oxide onto the inner wall of a titanium dioxide pore channel. Because the crystal transformation temperature of the silicon oxide is greatly higher than that of the titanium dioxide, the silicon oxide can not be changed when the titanium dioxide carries out crystal transformation under the high temperature and crystal grains grow. Therefore, the silicon oxide can play a supporting role, thereby keeping the mesoporous structure of the titanium dioxide and improving the thermal stability of the silicon oxide.
Description
Technical field
The present invention relates to a kind of method for preparing mesoporous TiO 2, particularly relate to the method that a kind of preparation has the mesoporous TiO 2 of high thermal stability.
Background technology
In recent years, along with the acceleration of global process of industrialization, problem of environmental pollution is on the rise, and the improvement of environment also more and more is subjected to people's extensive attention.Studies show that, utilize semi-conductive photocatalysis to degrade effectively and eliminate noxious pollutant.Titanium dioxide is current a kind of conductor photocatalysis material that application potential is arranged most, because of it has following characteristics: very high chemical stability, thermostability, chemical resistance, strong oxidizing property and nontoxic.Mesoporous TiO 2 is because of having high-specific surface area, orderly pore passage structure, aperture size is adjustable within the specific limits, the surface is easy to characteristics such as modification, can strengthen functions such as optically catalytic TiO 2, opto-electronic conversion effectively, make it show wide application prospect at aspects such as water treatment, purifying air, solar cell, nano material microreactor, biomaterials.
According to Chem.Int.Ed.Engl.1995,34 (18): 2014 the report, nineteen ninety-five mesoporous TiO 2 successfully prepared.Since then, the thermostability that how to improve mesoporous TiO 2 is perplexing the investigator always.In the mesoporous TiO 2 preparation process, need template is removed, adopt the incinerating way usually.Yet in calcination process, it is brilliant that unbodied titanium dioxide takes place to change, and causes caving in of duct, and specific surface area reduces rapidly, and meso-hole structure destroys.Therefore, how in the mesoporous TiO 2 preparation process, to keep its meso-hole structure not to be destroyed and become the technical issues that need to address of the present invention.
Summary of the invention
The objective of the invention is to, a kind of method that commercialization prepares mesoporous TiO 2 that is easy to is provided.
The said method for preparing mesoporous TiO 2 of the present invention, it comprises the steps:
(1) with titanium source, template and C
2～C
6Monohydroxy-alcohol places the reactor that has whipping appts, under agitation condition, adds dripping hydrochloric acid in this reactor, treat hydrochloric acid add after with the gained mixture in 50 ℃ static at least 24 hours, xerogel;
(2) will get powder in 1 hour～5 hours in 400 ℃～600 ℃ calcinings by the xerogel of step (1) gained, be target compound (being mesoporous TiO 2) after drying with gained powder after aqueous sodium hydroxide solution, water and the washing with alcohol successively;
Wherein: said titanium source is Ti (OR)
4, R is C
2～C
6Alkyl,
Said template is a compound shown in the formula I:
Among the formula I, R
1, R
2And R
3Independently be selected from C respectively
1～C
6Alkyl or C
1～C
6Alkoxyl group in a kind of; R
4, R
5And R
6Independently be selected from C respectively
1～C
20A kind of in the alkyl, and R
4, R
5And R
6In have at least one for carbonatoms more than or equal to 10 alkyl; N is 1～6 integer; X is Cl, Br or I.
Optimized technical scheme a: R of the present invention
1, R
2And R
3Independently be selected from C respectively
1～C
6Alkoxyl group in a kind of; Preferred technical scheme is: R
1, R
2And R
3Independently be selected from C respectively
1～C
3Alkoxyl group in a kind of; Best technical scheme is: R
1, R
2And R
3Be methoxy or ethoxy;
In another optimized technical scheme of the present invention: n is 1～3 integer;
In another optimized technical scheme of the present invention: preferred titanium source is: tetraethyl titanate, isopropyl titanate or tetrabutyl titanate.
In another optimized technical scheme of the present invention: R
4, R
5And R
6Independently be selected from C respectively
1～C
20A kind of in the alkyl, and R
4, R
5And R
6In have at least one for carbonatoms more than or equal to 18 alkyl.
Mean pore size by the mesoporous TiO 2 of above-mentioned preparation method preparation is 2.7nm, and specific surface area is greater than 160m
2/ g.
Description of drawings
Fig. 1 is the small angle X-ray diffraction spectrogram of embodiment 1 product;
Fig. 2 is the N of embodiment 1 product
2The adsorption/desorption curve;
Fig. 3 is the BJH pore size distribution curve of embodiment 1 product;
Fig. 4 is the transmission electron microscope photo of product, as we can see from the figure pore passage structure clearly.
Embodiment
The said method for preparing mesoporous TiO 2 of the present invention, it comprises the steps:
(1) with titanium source (preferred tetraethyl titanate, isopropyl titanate or tetrabutyl titanate), template (compound shown in the formula I) and C
2～C
6Monohydroxy-alcohol (preferred alcohol, Virahol or propyl carbinol) places the reactor that has whipping appts, under 15 ℃～25 ℃ and agitation condition, the hydrochloric acid that in this reactor, add to drip volumetric molar concentration and be 4M to system pH less than 2, treat hydrochloric acid add after with the gained mixture in 50 ℃ static at least 24 hours, xerogel;
Wherein: the mol ratio of template and titanium should be controlled at (0.05～1): 1, and best template (compound shown in the formula I) is 0.2:1 with the mol ratio of titanium.
(2) will be by the xerogel of step (1) gained in 400 ℃～600 ℃ calcinings after 1 hour～5 hours, with the cooling rate cool to room temperature (15 ℃～25 ℃) of 10 ℃/min powder (being silicon-titanium composite oxide).It is the aqueous sodium hydroxide solution of 2M～10M that gained powder (being silicon-titanium composite oxide) is placed volumetric molar concentration, washs 2～24 hours under 50 ℃ of conditions, and water and washing with alcohol successively promptly get target compound (mesoporous TiO 2) after drying then.
The present invention is when the preparation mesoporous TiO 2, and adopting silane compound (compound shown in the formula I) is template, and used silane compound forms silicon oxide when calcining, and it can born at titanium dioxide duct inwall.Because the brilliant temperature of the commentaries on classics of silicon oxide is far above titanium dioxide, when titanium dioxide at high temperature changeed brilliant and grain growing, silicon oxide then can not change.Therefore its (silicon oxide) can play the effect of support, thereby keeps the meso-hole structure of mesoporous TiO 2, improves the thermostability of mesoporous TiO 2.
Preparation method of the present invention, the raw material that it adopted (suc as formula compound shown in the I) wide material sources and cheap.In addition, preparation method's of the present invention operational condition gentleness and step are simple, are a kind of methods that commercialization prepares mesoporous TiO 2 that is easy to.
The present invention is further elaborated below by embodiment, and its purpose only is better to understand content of the present invention.Therefore, the cited case does not limit protection scope of the present invention.
Embodiment 1
3.2g triethoxysilylpropyl dimethyl stearyl chloride leach in the 60mL Virahol, is added the 10mL isopropyl titanate again, stir 1h after, the aqueous hydrochloric acid acid that under vigorous stirring, drips the 10.6mL volumetric molar concentration and be 4M to system pH less than 2.Dropwise the back and continue to stir 1h.Gained colloidal sol is poured in the culture dish, and 50 ℃ were worn out 1 day, and obtained xerogel.
The xerogel 4g that obtains, temperature programming in airflow, is warmed up to 400 ℃ of insulation 2h by 1 ℃/min.With the speed cool to room temperature of 10 ℃/min, obtain 1.45g white powder then.
Get the above-mentioned powder of 1g, put into the 10M aqueous sodium hydroxide solution, 50 ℃ of washing 2h, the back use 10mL water, ethanol respectively to wash three times, and dry 10h in 60 ℃ infrared obtains the white powder (target compound) of 0.86g.
The small angle X-ray diffraction spectrogram of target compound is seen Fig. 1, and as shown in Figure 1: there is diffraction peak in little angle XRD, illustrates that there is orderly meso-hole structure in target compound;
The N of target compound
2The adsorption/desorption curve is seen Fig. 2, and as shown in Figure 1: curve is the IV type, H
2Hysteresis loop illustrates that target compound is a meso-hole structure;
The BJH pore size distribution curve of target compound is seen Fig. 3, and as shown in Figure 3: curve is narrow and sharp, and target compound aperture homogeneous is described;
The transmission electron microscope photo of target compound is seen Fig. 4, as can see from Figure 4 pore passage structure clearly.
Embodiment 2
7.3g trimethoxy silicon propyl-dimethyl octadecyl ammonium chloride is dissolved in the 88mL propyl carbinol, adds the 10mL tetrabutyl titanate again, stir 1h after, the aqueous hydrochloric acid acid that under vigorous stirring, drips the 10.6mL volumetric molar concentration and be 4M to system pH less than 2.Dropwise the back and continue to stir 1h.Gained colloidal sol is poured in the culture dish, and 50 ℃ were worn out 1 day, and obtained xerogel.
The xerogel 4g that obtains, temperature programming in airflow, is warmed up to 500 ℃ of insulation 2h by 1 ℃/min.With the speed cool to room temperature of 10 ℃/min, obtain 1.16g white powder then.
Get the above-mentioned powder of 1g, put into the 5M aqueous sodium hydroxide solution, 50 ℃ of washing 24h, the back use 10mL water, ethanol respectively to wash three times, and dry 10h in 60 ℃ infrared obtains the white powder of 0.74g.
Embodiment 3
2.9g trimethoxy silicon propyl-dimethyl octadecyl ammonium chloride is dissolved in the 56mL dehydrated alcohol, adds the 10mL tetrabutyl titanate again, stir 1h after, the aqueous hydrochloric acid acid that under vigorous stirring, drips the 10.6mL volumetric molar concentration and be 4M to system pH less than 2.Dropwise the back and continue to stir 1h.Gained colloidal sol is poured in the culture dish, and 50 ℃ were worn out 1 day, and obtained xerogel.
The xerogel 4g that obtains, temperature programming in airflow, is warmed up to 600 ℃ of insulation 2h by 1 ℃/min.With the speed cool to room temperature of 10 ℃/min, obtain 1.96g white powder then.
Get the above-mentioned powder of 1g, put into the 2M aqueous sodium hydroxide solution, 50 ℃ of washing 10h, the back use 10mL water, ethanol respectively to wash three times, and dry 10h in 60 ℃ infrared obtains the white powder of 0.88g.
Claims (8)
1, a kind of method for preparing mesoporous TiO 2, it comprises the steps:
(1) with titanium source, template and C
2～C
6Monohydroxy-alcohol places the reactor that has whipping appts, under agitation condition, adds dripping hydrochloric acid in this reactor, treat hydrochloric acid add after with the gained mixture in 50 ℃ static at least 24 hours, xerogel;
(2) will get powder in 1 hour～5 hours in 400 ℃～600 ℃ calcinings by the xerogel of step (1) gained, be target compound with gained powder after aqueous sodium hydroxide solution, water and the washing with alcohol successively after drying;
Wherein: said titanium source is Ti (OR)
4, R is C
2～C
6Alkyl,
Said template is a compound shown in the formula I:
Among the formula I, R
1, R
2And R
3Independently be selected from C respectively
1～C
6Alkyl or C
1～C
6Alkoxyl group in a kind of; R
4, R
5And R
6Independently be selected from C respectively
1～C
20A kind of in the alkyl, and R
4, R
5And R
6In have at least one for carbonatoms more than or equal to 10 alkyl; N is 1～6 integer; X is Cl, Br or I.
2, the method for claim 1 is characterized in that, wherein R
1, R
2And R
3Independently be selected from C respectively
1～C
6Alkoxyl group in a kind of.
3, method as claimed in claim 2 is characterized in that, wherein R
1, R
2And R
3Independently be selected from C respectively
1～C
3Alkoxyl group in a kind of.
4, method as claimed in claim 3 is characterized in that, wherein R
1, R
2And R
3Be methoxy or ethoxy.
5, the method for claim 1 is characterized in that, wherein n is 1～3 integer.
6, the method for claim 1 is characterized in that, wherein said titanium source is: tetraethyl titanate, isopropyl titanate or tetrabutyl titanate.
7, the method for claim 1 is characterized in that, wherein R
4, R
5And R
6Independently be selected from C respectively
1～C
20A kind of in the alkyl, and R
4, R
5And R
6In have at least one for carbonatoms more than or equal to 18 alkyl.
8, as any described method of claim 1～7, it is characterized in that wherein the mol ratio of template and titanium is (0.05～1): 1.
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| CN200910047155XA CN101503212B (en) | 2009-03-06 | 2009-03-06 | Method for preparing mesoporous titanium dioxide |
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| CN101503212B CN101503212B (en) | 2010-09-29 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856610A (en) * | 2010-06-10 | 2010-10-13 | 沈阳化工大学 | Method for preparing silicon and zinc co-doped titanium dioxide mesoporous material |
| CN102875032A (en) * | 2011-07-15 | 2013-01-16 | 比亚迪股份有限公司 | Sol composition, preparation method thereof, method for forming self-cleaning and anti-reflective film on glass and self-cleaning and anti-reflective glass |
| CN103288090A (en) * | 2013-06-17 | 2013-09-11 | 华东理工大学 | Preparation method of cubic silicon dioxide shells |
| CN103691415A (en) * | 2013-12-18 | 2014-04-02 | 绍兴文理学院 | High-crystallinity titanium dioxide-silica nano composite material with regular mesoporous structure as well as preparation method and application thereof |
| CN105712395A (en) * | 2016-01-21 | 2016-06-29 | 华南理工大学 | Method for preparing large-specific-surface-area mesoporous TiO2 by using SiO2 in biomass |
| CN111699165A (en) * | 2018-02-14 | 2020-09-22 | 日本碍子株式会社 | Titanium dioxide porous body and method for producing same |
| CN112387260A (en) * | 2020-10-28 | 2021-02-23 | 东南大学 | Recyclable mesoporous TiO with adjustable surface electrical property2Adsorbent and preparation method and application thereof |
| CN113206199A (en) * | 2021-05-08 | 2021-08-03 | 海宁万发新材料有限公司 | Perovskite solar cell electronic transmission layer and preparation method thereof |
-
2009
- 2009-03-06 CN CN200910047155XA patent/CN101503212B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856610A (en) * | 2010-06-10 | 2010-10-13 | 沈阳化工大学 | Method for preparing silicon and zinc co-doped titanium dioxide mesoporous material |
| CN102875032A (en) * | 2011-07-15 | 2013-01-16 | 比亚迪股份有限公司 | Sol composition, preparation method thereof, method for forming self-cleaning and anti-reflective film on glass and self-cleaning and anti-reflective glass |
| CN102875032B (en) * | 2011-07-15 | 2015-09-02 | 比亚迪股份有限公司 | Sol composition and preparation method thereof, form the method for self-cleaning anti-reflection film and self-cleaning anti-reflective glass at glass surface |
| CN103288090A (en) * | 2013-06-17 | 2013-09-11 | 华东理工大学 | Preparation method of cubic silicon dioxide shells |
| CN103288090B (en) * | 2013-06-17 | 2015-03-25 | 华东理工大学 | Preparation method of cubic silicon dioxide shells |
| CN103691415B (en) * | 2013-12-18 | 2016-10-12 | 绍兴文理学院 | High-crystallinity, rule the titania-silica nano-complex of meso-hole structure, preparation method and applications |
| CN103691415A (en) * | 2013-12-18 | 2014-04-02 | 绍兴文理学院 | High-crystallinity titanium dioxide-silica nano composite material with regular mesoporous structure as well as preparation method and application thereof |
| CN105712395A (en) * | 2016-01-21 | 2016-06-29 | 华南理工大学 | Method for preparing large-specific-surface-area mesoporous TiO2 by using SiO2 in biomass |
| CN105712395B (en) * | 2016-01-21 | 2018-09-14 | 华南理工大学 | It is a kind of to utilize SiO in biomass2Prepare high specific surface area and mesoporous TiO2Method |
| CN111699165A (en) * | 2018-02-14 | 2020-09-22 | 日本碍子株式会社 | Titanium dioxide porous body and method for producing same |
| US11772983B2 (en) | 2018-02-14 | 2023-10-03 | Ngk Insulators, Ltd. | Titania porous body and method for producing same |
| CN112387260A (en) * | 2020-10-28 | 2021-02-23 | 东南大学 | Recyclable mesoporous TiO with adjustable surface electrical property2Adsorbent and preparation method and application thereof |
| CN112387260B (en) * | 2020-10-28 | 2022-06-03 | 东南大学 | Recyclable mesoporous TiO with adjustable surface electrical property2Adsorbent and preparation method and application thereof |
| CN113206199A (en) * | 2021-05-08 | 2021-08-03 | 海宁万发新材料有限公司 | Perovskite solar cell electronic transmission layer and preparation method thereof |
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|---|---|
| CN101503212B (en) | 2010-09-29 |
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